Due to the unique structure and active reactive performances of allene compounds as well as their more and more important role played in the organic syntheses, the allene chemistry has attracted more and more attentions (S. Yu, S. Ma, Angew. Chem., Int. Ed. 2012, 51, 3074; M. A. Tius, Chem. Soc. Rev. 2014, 43, 2979; J. L. Bras, J. Muzart, Chem. Soc. Rev. 2014, 43, 3003; S. Kitagaki, F. Inagaki, C. Mukai, Chem. Soc. Rev. 2014, 43, 2956; M. P. Muñoz, Chem. Soc. Rev. 2014, 43, 3164; C. S. Adams, C. D. Weatherly, E. G. Burke, J. M. Schomaker Chem. Soc. Rev. 2014, 43, 3136; R. Zimmer, H. U. Reissig, Chem. Soc. Rev., 2014, 43, 2888; m) W. Yang, A. S. K. Hashmi, Chem. Soc. Rev., 2014, 43, 2941; B. Alcaide, P. Almendros, C. Aragoncillo, Chem. Soc. Rev. 2014, 43, 3106; T. Cañeque, F. M. Truscott, R. Rodriguez, G. Maestri, M. Malacria, Chem. Soc. Rev. 2014, 43, 2916; F. López, J. L. Mascareñas, Chem. Soc. Rev. 2014, 43, 2904; Z. Wang, X. Xu, O. Kwon, Chem. Soc. Rev. 2014, 43, 2927). Therefore, how to simply and efficiently synthesize various allene compounds, especially 1,3-disubstituted allenes having an axial chirality activity, has become one of the issues of increasing concern to the chemists (L. K. Sydnes, Chem. Rev. 2003, 103, 1133; N. Krause, A. Hoffmann-Röder, Tetrahedron 2004, 60, 11671; K. M. Brummond, J. E. Deforrest, Synthesis 2007, 795; M. Ogasawara, Tetrahedron: Asymmetry 2009, 20, 259; g) S. Yu, S. Ma, Chem. Commun., 2011, 47, 5384). The earlier synthetic methods of optically active 1,3-substituted allenes require the use of hazardous chemicals such as n-butyl lithium or ethyl magnesium bromide and lithium aluminum hydride, and the operations are inconvenient, which were unbeneficial to the large scale synthesis (L.-I. Olsson, A. Claesson, Acta Chem. Scand. 1977, B31, 614; A. Claesson, L.-I. Olsson, J. Am. Chem. Soc. 1979, 101, 7302; R. A. Smith, R. L. White, A. Krantz, J. Med. Chem. 1988, 31, 1558; J. Stichler-Bonaparte, H. Kruth, R. Lunkwitz, C. Tschierske, Liebigs Ann. 1996, 1375). Recently our team developed a series of processes for synthesizing optically active 1,3-disubstituted allenes by using terminal alkynes, aldehydes and chiral amines under the promotion of a zinc salt or under the co-promotion of a zinc salt and a monovalent copper salt. Although these processes have made great progress compared to the traditional methods, there are still some shortcomings such as a narrow substrate range, the requirement of large amount of metallic salts, going through a multi-step operation of the protection and deprotection for some specific functional groups (J. Ye, S. Li, B. Chen, W. Fan, J. Kuang, J. Liu, Y. Liu, B. Miao, B. Wan, Y. Wang, X. Xie, Q. Yu, W. Yuan, S. Ma, Org. Lett. 2012, 14, 1346; J. Ye, W. Fan, S. Ma, Chem. Eur J. 2013, 19, 716; J. Ye, R. Lu, W. Fan, S. Ma, Tetrahedron 2013, 69, 8959; R. Lü, J. Ye, T. Cao, B. Chen, W. Fan, W. Lin, J. Liu, H. Luo, B. Miao, S. Ni, X. Tang, N. Wang, Y. Wang, X. Xie, Q. Yu, W. Yuan, W. Zhang, C. Zhu, S. Ma, Org. Lett. 2013, 15, 2254).
The present invention overcomes all the drawbacks of the prior arts, which provides a one-step process for simply and efficiently preparing highly optically active 1,3-disubstituted allenes by using a divalent copper salt as the catalyst and using a terminal alkyne and chiral α,α-diphenyl prolinol as reactants.